In‐situ Chemiluminescence‐Driven Reversible Addition–Fragmentation Chain‐Transfer Photopolymerization

Watuthanthrige, Nethmi De Alwis; Allegrezza, Michael L.; Dolan, Madison T.; Kloster, Alex J.; Kovaliov, Marina; Averick, Saadyah; Konkolewicz, Dominik

doi:10.1002/anie.201905317

Cited by 19 publications

(21 citation statements)

References 34 publications

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“…29 More recently, Konkolewicz et al have developed a biphasic approach for the synthesis of well-defined functional polymers terminated by RAFT agents, where CL reactions and photopolymerization processes occur in the organic and aqueous phases, respectively. 30 At present, the reported CL-induced photopolymerizations are exclusively based on the free radical mechanism. Cationic photopolymerization has attracted more and more attention due to its unique features, including lack of oxygen inhibition, low toxicity, irritation, "'postcuring"' in the dark, and high mechanical performance of the photocured materials with low shrinkage.…”

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confidence: 99%

“…Barner-Kowollik et al elegantly made use of the CL reaction as an efficient energy source for photoinitiated free radical polymerization as well as [2 + 2] photocycloaddition . More recently, Konkolewicz et al have developed a biphasic approach for the synthesis of well-defined functional polymers terminated by RAFT agents, where CL reactions and photopolymerization processes occur in the organic and aqueous phases, respectively …”

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confidence: 99%

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Chemiluminescence Induced Cationic Photopolymerization Using Sulfonium Salt

Wang

Meng

et al. 2020

ACS Macro Lett.

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A visible light cationic photoinitiating system under chemiluminescence irradiation using sulfonium salt is reported. The visible light emitted from the chemiluminescence reactions, absorbed by the sulfonium salt, essentially leads to the formation of protonic acids capable of initiating cationic polymerization of oxirane and vinyl monomers. The process is suitable for the formation of linear polymer chains as well as cross-linked functional networks with aggregationinduced emission property. Notably, high "post polymerization" efficiency in dark (∼20%) was observed, which can compensate the limited chemiluminescence fluorescence efficiency and favors to increase the conversion.

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Chemiluminescence Induced Cationic Photopolymerization Using Sulfonium Salt

Wang

Meng

et al. 2020

ACS Macro Lett.

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“…In particular, optical density can be an issue in photochemical reactions. Although innovative approaches such as flow chemistry set-ups − or combining chemiluminescent processes with photochemical RAFT systems could reduce the impact of optical density. However, most PET-RAFT systems are still performed as batch reactions.…”

Section: Practical Considerations and Implementation Of Pet-raftmentioning

confidence: 99%

PET-RAFT Polymerization: Mechanistic Perspectives for Future Materials

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In the past decade, photochemistry has emerged as a growing area in organic and polymer chemistry. Use of light to drive polymerization has advantages by imparting spatial and temporal control over the reaction. Photoinduced electron/energy transfer reversible addition−fragmentation chain transfer polymerization (PET-RAFT) has emerged as an excellent technique for developing well-defined polymers from a variety of functional monomers. However, the mechanism, of electron versus energy transfer is debated in the literature, with conflicting reports on the underlying process. This perspective focuses on the mechanistic aspects of PET-RAFT, in particular, the electron versus energy transfer pathways. The different mechanisms are evaluated, including evidence for one versus the other mechanisms. The current literature has not reached a consensus across all PET-RAFT processes, but rather, each catalytic system has unique characteristics.

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“…Recent work with chemiluminescence as a light source for activating photoinitiated RAFT has offset some www.advancedsciencenews.com www.advancedscience.com of these limitations, where in situ light generation can be used to increase irradiation uniformity. [49,50]…”

Section: Indirect Photoactivationmentioning

confidence: 99%

Progress and Perspectives Beyond Traditional RAFT Polymerization

et al. 2020

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The development of advanced materials based on well-defined polymeric architectures is proving to be a highly prosperous research direction across both industry and academia. Controlled radical polymerization techniques are receiving unprecedented attention, with reversible-deactivation chain growth procedures now routinely leveraged to prepare exquisitely precise polymer products. Reversible addition-fragmentation chain transfer (RAFT) polymerization is a powerful protocol within this domain, where the unique chemistry of thiocarbonylthio (TCT) compounds can be harnessed to control radical chain growth of vinyl polymers. With the intense recent focus on RAFT, new strategies for initiation and external control have emerged that are paving the way for preparing well-defined polymers for demanding applications. In this work, the cutting-edge innovations in RAFT that are opening up this technique to a broader suite of materials researchers are explored. Emerging strategies for activating TCTs are surveyed, which are providing access into traditionally challenging environments for reversible-deactivation radical polymerization. The latest advances and future perspectives in applying RAFT-derived polymers are also shared, with the goal to convey the rich potential of RAFT for an ever-expanding range of high-performance applications.

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In‐situ Chemiluminescence‐Driven Reversible Addition–Fragmentation Chain‐Transfer Photopolymerization

Cited by 19 publications

References 34 publications

Chemiluminescence Induced Cationic Photopolymerization Using Sulfonium Salt

Chemiluminescence Induced Cationic Photopolymerization Using Sulfonium Salt

PET-RAFT Polymerization: Mechanistic Perspectives for Future Materials

Progress and Perspectives Beyond Traditional RAFT Polymerization

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